1,3-diamino-4-(aminomethyl) - benzene derivatives and colorants containing the said compounds

ABSTRACT

1,3-Diamino-4-(aminomethyl)-benzene derivatives of the general Formula (I) or their physiologically tolerated, water-soluble salts,  
                 
 
     as well as agents for the oxidative dyeing of fibers, containing these compounds.

[0001] The invention relates to the new1,3-diamino-4-(aminomethyl)-benzene derivatives, as well as to agentscontaining these compounds, for dyeing keratin fibers.

[0002] In the field of dyeing keratin fibers, especially of dyeing hair,oxidation dyes have achieved a significant importance. The dyeing isbrought about here by the reaction of certain developer substances withcertain coupler substances in the presence of a suitable oxidizingagent. As developer substances, 2,5-diaminotoluene,2,5-diaminophenylethyl alcohol, p-aminophenol, 1,4-diaminobenzene and4,5-diaminopyrazole-1-(2-hydroxyethyl) and, as coupler substances,resorcinol, 2-methyl-resorcinol, 1-naphthol, 3-aminophenol,m-phenylene-diamine, 2-amino-4-(2′-hydroxyethyl)amino-anisole,1,3-diamino-4-(2′-hydroxyethoxy)benzene and2,4-diamino-5-fluoro-toluene, for example, are named here.

[0003] Oxidation dyes, which are used to dye human hair, must meetnumerous requirements in addition to dyeing the hair in the desiredintensity. For example, the dyes must be safe from toxicological anddermatological points of view the dyeings achieved must exhibit goodlight fastness, permanent waving fastness, acid fastness and crockingfastness. In any case, however, such dyeings must remain stable over aperiod of at least 4 to 6 weeks without the action of light, rubbing andchemical agents. In addition, it is necessary that a broad range ofdifferent color nuances can be produced by combinations of suitabledeveloper substances and coupler substances.

[0004] An attempt has already been made to improve the properties ofm-phenylenediamines by the introduction of substituents. In thisconnection, reference is made to the German Offenlegungsschriften 35 08309 and 38 24 299, from which the use of 5-substitutedm-phenylenediamines in oxidation hair-dyeing agents is known. Moreover,from the EP OS 0 740 931, the use of 1-substituted m-phenylenediaminesin oxidation hair-dyeing agents is known. However, with the dyeingagents known at the present time, it is not possible to fulfill therequirements, which must be met by a dyeing agent, in all respects. Forthis reason, there continues to be a need for new developer substances,which fulfill the above-mentioned requirements particularly well.

[0005] It has now been found that, if1,3-diamino-4-(aminomethyl)-benzene derivatives of the general Formula(I) are used, intensive, stable, blue color nuances are obtained.

[0006] An object of the present invention therefore are1,3-diamino-4-(aminomethyl)-benzene derivatives of the general Formula(I) or their physiologically tolerated, water-soluble salts,

[0007] wherein

[0008] R1 and R2 independently of one another are hydrogen, a C₁-C₆alkyl group, a C₂-C₄ hydroxyalkyl group or a C₃-C₄ dihydroxyalkyl group,

[0009] R3 is hydrogen or a C₁-C₄ alkyl group,

[0010] R4 and R5 independently of one another are hydrogen, a C₁-C₂alkoxy group, a saturated C₁-C₆ alkyl group, an unsaturated C₃-C₆ alkylgroup, a C₂-C₄ hydroxyalkyl group, a C₃-C₄ dihydroxyalkyl group, a C₂-C₄aminoalkyl group, a C₂-C₄ dimethylaminoalkyl group, a C₂-C₄acetylaminoalkyl group, a C₂-C₄ methoxyalkyl group, a C₂-C₄ ethoxyalkylgroup, a C₁-C₄ cyanoalkyl group, a C₁-C₄ carboxyalkyl group, a C₁-C₄aminocarbonylalkyl group, a pyridylmethyl group, a furfuryl group, athienyl methyl group, a substituted pyridyl group or a group of Formula(II)

[0011] or R4 and R5 together with the nitrogen atom form a ring ofFormula

[0012] R6, R7, R8, R9 and R10 independently of one another representhydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxy group,a C₁-C₄ alkoxy group, a C₂-C₄ hydroxyalkoxy group, a C₁-C₆ alkyl group,a C₁-C₄ alkyl thioether group, a mercapto group, a nitro group, an aminogroup, an alkylamino group, a di(C₁-C₆ alkyl)amino group, adihydroxy-(C₃-C₄)alkyl)amino group, a di(C₁-C₄ hydroxyalkyl)amino group,a (C₁-C₄ hydroxyalkyl)-(C₁-C₆ alkyl)-amino group, a trifluoromethanegroup, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, an —Si(CH₃)₃group, a C₁-C₄ hydroxyalkyl group, a C₂-C₄ dihydroxyalkyl group, acarboxy group or a pyrrolidine group or two R6 to R10 groups, adjacentto one another, form an —O—CH2-O link,

[0013] R11 is hydrogen, a hydroxy group, a carboxy group, anaminocarbonyl group or a hydroxymethyl group;

[0014] R12 is hydrogen or a C₁-C₆ alkyl group; and

[0015] n is 0 or 1.

[0016] As suitable compounds of Formula (I), the following compounds,for example, may be named: 1,3-diamino-4-(methylamino-methyl)-benzene,1,3-diamino-(4-allylaminomethyl)-benzene,2-(2,4-diamino-benzylamino)-ethanol,1,3-diamino-4-(pyrrolidine-1-ylmethyl)-benzene,1-(2,4-diamino-benzyl)-pyrrolidine-3-ol,[1-(2,4-diaminobenzyl)-pyrrolidine-2-yl]-methanol,1,3-diamino-4-[(2-aminoethylamino)-methyl]-benzene,1,3-diamino-4-morpholine-4-ylmethyl-benzene,1-(2,4-diaminobenzyl)-piperidine-4-ol,1-(2,4-diaminobenzyl)-piperidine-3-ol,N-[2-(2,4-diamino-benzylamino)-ethyl]-acetamide,3-[2-(2,4-diaminobenzylamino)-1-hydroxyethyl]-phenol,1,3-diamino-4-[(2-methoxyethylamino)-methyl]-benzene,2-(2,4-diaminobenzylamino)-propane-1-ol,1,3-diamino-4-{[(tetrahydrofuran-2-ylmethyl)-amino]-methyl}-benzene,1,3-diamino-4-((2-aminophenylamino)-methyl)-benzene,1,3-diamino-4-((3-aminophenyl-amino)-methyl)-benzene,1,3-diamino-4-((2-hydroxyphenylamino)-methyl)-benzene,1,3-diamino-4-((3-hydroxyphenylamino)-methyl)-benzene,1,3-diamino-4-((2-hydroxyphenylamino)-methyl)-benzene,1,3-diamino-4-((4-hydroxyphenylamino)-methyl)-benzene and1,3-diamino-4-((4-methyl-phenylamino)-methyl)-benzene.

[0017] Compounds of Formula (I), in which (i) one or more or all of theR1, R2 and R3 groups are hydrogen and/or (ii) one of the R4 or R5 groupsis a C₂-C₄ hydroxyalkyl group, an unsaturated C₃-C₆ alkyl group, a C₂-C₄aminoalkyl group or a C₁-C₄ alkyl group, are preferred.

[0018] Especially the following compounds of Formula (I) are preferred:1,3-diamino-4-(methylaminomethyl)-benzene,1,3-diamino-(4-allyl-aminomethyl-benzene,2-(2,4-diaminobenzylamino)-ethanol and1,3-diamino-4-[(2-aminoethylamino)-methyl]-benzene.

[0019] The 1,3-diamino-4-(aminomethyl)-benzene derivatives of Formula(I) can be used as free bases as well as in the form of theirphysiologically tolerated salts with inorganic or organic acids such ashydrochloric acid, sulfuric acid, phosphoric acid, acetic acid,propionic acid, lactic acid or citric acid.

[0020] The inventive diaminobenzene derivatives of Formula (I) can besynthesized using known methods. For example, the synthesis of theinventive compounds can be carried out as follows:

[0021] a reductive amination of a substituted benzene of Formula (IIIwith an amine having the formula NHR4R5

[0022] the protective group being split off subsequently,

[0023] in which

[0024] Ra represents a protective group, such as those described in thechapter “Protective Groups” in Organic Synthesis, chapter 7, WileyInterscience, 1991,

[0025] Rb represents NR2Ra and

[0026] R2, R3, R4 and R5 have the meanings given in Formula (I).

[0027] The inventive 1,3-diamino-4-(aminomethyl)-benzene derivatives ofFormula (I) are readily soluble in water and make dyeings possible witha high color intensity and an excellent color fastness, especially asfar as the light fastness, washing fastness and crocking fastness areconcerned. The compounds of Formula (I) furthermore have an excellentshelf life, especially as a component of the dyeing agent describedbelow.

[0028] Agents for the oxidative dyeing of keratin fibers, such as hair,fur, feathers or wool, especially of human hair, based on a combinationof a developer substance and a coupler substance, which contain at leastone 1,3-diamino-4-(aminomethyl) benzene derivatives of Formula (I), aretherefore a further object of the present invention.

[0029] The 1,3-diamino 4-(aminomethyl)-benzene derivatives of Formula(I) are contained in the inventive dyeing agent in an amount of about0.005 to 20 percent by weight, an amount of about 0.01 to 5.0 percent byweight and especially of 0.1 to 2.5 percent by weight being preferred.

[0030] As developer substances, preferably 1,4-diamino-benzene(p-phenylenediamine), 1,4-diamino-2-methyl-benzene (p-toluylenediamine),1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-3,5-diethyl-benzene,1,4-diamino-2,5-dimethyl-benzene, 1,4-diamino-2,3-dimethyl-benzene,2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophene-2-yl)-benzene,1,4-diamino-2-(thiophene-3-yl)-benzene, 1,4-diamino-2-(pyridine-3-yl)-benzene, 2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethyl-benzene,1,4-diamino-2-aminomethyl-benzene, 1,4-diamino-2-hydroxymethyl-benzene,1,4-diamino-2-(2-hydroxyethoxy)-benzene,2-(2-acetylamino)ethoxy)-1,4-diaminobenzene, 4-phenylamino-aniline,4-dimethylamino-aniline, 4-diethylamino-aniline,4-dipropylamino-aniline, 4-[ethyl(2-hydroxyethyl)-amino]-aniline,4-[di(2-hydroxyethyl)amino]-aniline,4-[di(2-hydroxyethyl)-amino]-2-methyl-aniline,4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxy-propyl)amino]-aniline,4-[(2,3-dihydroxypropyl)amino]-aniline,1,4-diamino-2-(1-hydroxyethyl)-benzene,1,4-diamino-2-(2-hydroxyethyl)-benzene,1,4-diamino-2-(1-methylethyl)-benzene,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis[(4-aminophenyl)amino]-butane, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-phenol,4-amino-3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol,4-amino-3-fluoro-phenol, 4-methylamino-phenol,4-amino-2-(aminomethyl)-phenol, 4-amino-2-(hydroxymethyl)-phenol,4-amino-2-fluoro-phenol,4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol,4-amino-2-methyl-phenol, 4-amino-2-(methoxymethyl)-phenol,4-amino-2-(2-hydroxyethyl)-phenol, 5-amino-salicylic acid,2,5-diamino-pyridine, 2,4,5,6-tetraamino-pyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-amino-phenol,2-amino-6-methyl-phenol, 2-amino-5-methyl-phenol and1,2,4-trihydroxy-benzene come into consideration.

[0031] Furthermore, in addition to the compounds of Formula (I), theinventive dyeing agent may contain further, known, coupler substances,such as N-(3-dimethylamino-phenyl)-urea, 2,6-diamino-pyridine,2-amino-4-[(2-hydroxyethyl)amino]-anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene,2,3-diamino-6-methoxy-pyridine,3-amino-6-methoxy-2-(methylamino)-pyridine,2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)-benzene,1,3-diamino-4-(3-hydroxy-propoxy)-benzene,1,3-diamino-4-(2-methoxyethoxy)-benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene,2,4-diamino-phenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]-aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene,5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline,3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane,di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene,2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole,3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol,5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methyl-phenol,3-amino-2-chloro-6-methyl-phenol, 3-aminophenol,2-[(3-hydroxyphenyl)-amino]-acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methyl-phenol,5-[(2-hydroxyethyl)amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxy-phenol,2-(4-amino-2-hydroxyphenoxy)-ethanol,5-[(3-hydroxypropyl)amino]-2-methyl-phenol,3-[(2,3-dihydroxypropyl)-amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine,2,6-dihydroxy-3,4-dimethyl-pyridine, 5-amino-4-chloro-2-methyl-phenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy-naphthalene,1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene,2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene,2-chloro-1,3-dihydroxy-benzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxy-phenol, 3,4-methylenedioxy-aniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole,6-hydroxy-indole, 7-hydroxy-indole and 2,3-indolindione.

[0032] The coupler substances and the developer substances may becontained in the inventive dyeing agent in each case individually or inadmixture with one another, the total amount of coupler substances andthe developer substances in the inventive dyeing agent in each casebeing about 0.005 to 20 percent by weight, preferably of about 0.01 to 5percent by weight and particularly of 0.1 to 2.5 percent by weight,based on the total amount of the dyeing agent,

[0033] The total amount of the combination of developer substance andcoupler substance, contained in the dyeing agent described here,preferably is about 0.01 to 20 percent by weight, an amount of about0.02 to 10 percent by weight and, in particular, of 0.2 to 6 percent byweight being especially preferred. The developer substances and couplersubstances generally are used in about equimolar amounts; however, it isnot disadvantageous if the developer substances in this respect are in adifferent proportion to the coupler substances.

[0034] Furthermore, the inventive dyeing agent may additionally containother dye components, such as 6-amino-2-methylphenol and2-amino-5-methylphenol, as well as conventional, substantive dyes, forexample, triphenylmethane dyes such as4-[(4′-aminophenyl)-(4′-imino-2″,5″-cyclohexadiene-1″-ylidene)-methyl]-2-methylaminobenzenemonohydrochloride (C.I. 42 510) and4-[(4′-amino-3′-methyl-phenyl)-(4″-imino-3″-methyl-2″,5″-cyclohexadiene-1″-ylidene)-methyl]-2-methylaminobenzenemonohydrochloride (C.I. 42 520), aromatic nitro dyes, such as4-(2′-hydroxyethyl)amino-nitrotoluene, 2-amino-4,6-dinitrophenol,2-amino-5-(2′-hydroxyethyl)amino-nitrobenzene,2-chloro-6-(ethylamino)-4-nitrophenol,4-chloro-N-(2-hydroxyethyl)-2-nitroaniline,5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol and1-[(2′-ureidoethyl)amino-4-nitrobenzene, azo dyes, such as sodium6-[(4′-aminophenyl)azo]-5-hydroxy-naphthalene-1 sulfonate (C.I. 14 805)and dispersion dyes, such as, for example, 1,4-diaminoanthraquinone and1,4,5,8-tetraaminoanthraquinone. The dyeing agents may contain these dyecomponents in and amount of about 0.1 to 4 percent by weight.

[0035] Of course, the coupler substances and developer substances, aswell as the other dye components, if they are bases, can also be used inthe form of their physiologically tolerated salts with organic orinorganic acids, such as hydrochloric acid or sulfuric acid, or, if theyhave aromatic OH groups, in the form of their salts with the bases, forexample, as alkali phenolates.

[0036] Furthermore, if the dyeing agents are used to dye hair, they maycontain further, conventional, cosmetic additives, for example,antioxidants, such as ascorbic acid, thioglycolic acid or sodiumsulfite, as well as perfume oils, complexing agents, wetting agents,emulsifiers, thickeners and care materials.

[0037] The inventive dyeing agents may be prepared, for example, in theform of a solution, especially an aqueous or aqueous alcoholic solution.However, preparations in the form of a cream, a gel or an emulsion areparticularly preferred. Their composition represents a mixture of thedye components with additives, customarily used for such preparations.

[0038] Additives, customarily used in solutions, creams, emulsions orgels, are, for example, solvents such as water, low molecular weightaliphatic alcohols, such as ethanol, propanol or isopropanol, glycerinor glycols such as 1,2-propylene glycol, furthermore wetting agents oremulsifies from the classes of anionic, cationic, amphoteric or nonionicsurface-active substances, such as fatty alcohol sulfates, ethoxylatedfatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkyl betaines, ethoxylated fattyalcohols, ethoxylated nonylphenols, fatty acid alkanolamides andethoxylated fatty esters, furthermore, thickeners such as highermolecular weight fatty alcohols, starch, cellulose derivatives,petrolatum, paraffin oil and fatty acids, as well as, in addition, carematerials such as cationic resins, lanolin derivatives, cholesterol,pantothenic acid and betaine. The components mentioned are used inamounts, customary for such purposes; for example, the wetting agentsand emulsifies are used in concentrations of about 0.5 to 30 percent byweight, the thickeners in an amount of about 0.1 to 30 percent by weightand the care materials in a concentration of about 0.1 to 5 percent byweight.

[0039] Depending on the composition, the inventive dyeing agent may beslightly acidic, neutral or alkaline. In particular, it has a pH ofabout 6.5 to 11.5, the adjustment to an alkaline value preferably beingmade with ammonia. However, organic amines, such as monoethanolamine andtriethanolamine or also inorganic bases, such as sodium hydroxide andpotassium hydroxide, may also be used. For adjusting the pH to an acidicvalue, inorganic or organic acids, such as phosphoric acid, acetic acid,citric acid or tartaric acid, come into consideration.

[0040] If used for the oxidation dyeing of hair, the dyeing agent,described above, is mixed immediately before use with an oxidizingagent. This mixture is applied on the hair in an amount, which issufficient for the treatment of the hair and depends on the fullness ofthe hair and generally ranges from about 60 to 200 gram.

[0041] As oxidizing agent for developing the dyeing of the hair, mainlyhydrogen peroxide or its addition compounds with urea, melamine, sodiumborate or sodium carbonate in the form of a 3 percent to 12 percent andpreferably 6 percent aqueous solution, but also the oxygen from the aircome into consideration. If a 6 percent hydrogen peroxide solution isused as oxidizing agent, the ratio by weight of the dyeing agent tooxidizing agent is 5:1 to 1:2 and preferably, however, 1:1. Largeramounts of oxidizing agent are used especially if the concentration ofdye in the hair-dyeing agent is greater or if, at the same time, it isintended to bleach the hair more. The mixture is allowed to react withthe hair for about 10 to 45 minutes and preferably for 30 minutes at atemperature of 15° to 50° C. The hair is then rinsed with water anddried. Optionally, after this rinsing, the hair is washed with a shampooand possibly rinsed with a weak organic acid, such as citric acid ortartaric acid and subsequently dried.

[0042] The inventive dyeing agents, containing 1,3-diamino-4-(aminomethyl)-benzene derivatives of Formula (I) as coupler substances make itpossible to dye hair with excellent color fastness, especially as far asthe light fastness, wash fastness and crocking fastness is concerned.With respect to the dyeing properties, the inventive hair-dyeing agentoffers a broad range of different color nuances, which depend on thenature and composition of the color components and extend from blond tobrown, purple, violet, blue and black color shades. The color shades aredistinguished here by their special color intensity. The very gooddyeing properties of the dyeing agents of the present application arefurthermore distinguished owing to the fact that these agents make itpossible to dye keratin fibers, especially human hair, which has notpreviously been damaged chemically and has turned gray, without anyproblems and with a good covering power.

[0043] The following examples are intended to explain the object of theinvention in greater detail, without limiting it.

EXAMPLES Example 1

[0044] Synthesis of 1,3-diamino-4-(aminomethyl)-benzenes

[0045] (General Synthesis Method)

[0046] A. Synthesis of t-butyl(3-t-butoxycarbonylamino-4-formyl-phenyl)-carbamate

[0047] 2,4-Diamino-benzaldehyde (2.75 g, 0.02 moles) and 8.7 g (0.04moles) of di-t-butyl dicarbonate are dissolved in a mixture of 50 mL of2N sodium hydrogen carbonate and 120 mL of acetonitrile. The reactionmixture is stirred for 20 hours. Subsequently, the reaction mixture ispoured into water and extracted twice with 100 mL of ethyl acetate. Thecombined extracts are extracted with dilute hydrochloric acid, thendried with magnesium sulfate and evaporated. The residue subsequently isrecrystallized from ethyl acetate.

[0048] t-Butyl (3-t-butoxycarbonylamino-4-formyl-phenyl)-carbamate (4.5g, 67 percent of the theoretical) is obtained.

[0049] B. 1,3-Diamino-4-(aminomethyl)-benzene derivatives

[0050] t-Butyl (3-t-butoxycarbonylamino-4-formyl-phenyl-carbamate (0.033g, 0.1 mmole) from step A and 0.15 mmole of the corresponding amine aredissolved in 1,2-dichloroethane. Subsequently, 0.1 mL of acetic acidsolution (1 M in 1,2-dichloroethane) and 0.06 g (0.3 mmoles) ofNaBH(OAc)₃ are added and the reaction mixture is stirred for 5 to 15hours at room temperature. At the end of the reaction, the reactionmixture is poured into 10 mL of ethyl acetate, the organic phase isextracted with sodium hydrogen carbonate and then dried with magnesiumsulfate. The solvent is distilled off in a rotary evaporator and theresidue purified on silica gel with a 9:1 mixture of petroleum ether andethyl acetate. The product, so obtained, is heated to 50° C. in 4 mL ofethanol.

[0051] Subsequently, to synthesize the hydrochloride, 1.5 mL of a 2.9molar ethanolic hydrochloric acid solution is added dropwise. Theprecipitate is filtered off, washed twice with 1 mL of ethanol and thendried.

[0052] a. 1,3-Diamino-4-(methylaminomethyl)-benzene hydrochloride

[0053] Amine used: methylamine

[0054] Mass spectrum: MH⁺ 152 (100)

[0055] b. 1.3-Diamino-4-(allylaminomethyl)-benzene hydrochloride

[0056] Amine used: allylamine

[0057] Mass spectrum: MH⁺ 178 (100)

[0058] c. 2-(2,4-Diaminobenzylamino)-ethanol hydrochloride

[0059] Amine used: ethanolamine

[0060] Mass spectrum: MH⁺ 182 (100)

[0061] d. 1,3-Diamino-4-(pyrrolidine-1-ylmethyl)-benzene hydrochloride

[0062] Amine used: pyrrolidine

[0063] Mass spectrum: MH⁺ 192 (100)

[0064] e. 1-(2,4-Diaminobenzyl)-pyrrolidine-3-ol hydrochloride

[0065] Amine used: 3-pyrrolidinol

[0066] Mass spectrum: MH⁺ 208 (100)

[0067] f. [1-(2,4-Diaminobenzyl)-pyrrolidine-2-yl]-methanolhydrochloride

[0068] Amine used: prolinol

[0069] Mass spectrum: MH⁺ 222 (100)

[0070] g. 1,3-Diamino-4-[(2-amino-ethylamino)-methyl]-benzenehydrochloride

[0071] Amine used: ethylenediamine

[0072] Mass spectrum: MH⁺ 181 (100)

[0073] h. 1,3-Diamino-4-(morpholine-4-ylmethyl)-benzene hydrochloride

[0074] Amine used: morpholine

[0075] Mass spectrum: MH⁺ 208 (100)

[0076] i. 1-(2,4-Diaminobenzyl)-piperidine-4-ol hydrochloride

[0077] Amine used: 4-hydroxy-piperidine

[0078] Mass spectrum: MH⁺ 222 (100)

[0079] j. 1-(2,4-diamino-benzyl)-piperidine-3-ol hydrochloride

[0080] Amine used: 3-hydroxy-piperidine

[0081] Mass spectrum: MH⁺ 222 (100)

[0082] k. N-[2-(2,4-diaminobenzylamino)-ethyl]-acetamide hydrochloride

[0083] Amine used: N-acetyl-ethylenediamine

[0084] Mass spectrum: MH⁺ 223 (100)

[0085] l. 1,3-Diamino-4-[(2-methoxyethylamino)-methyl]-benzenehydrochloride

[0086] Amine used: 2-methoxyethylamine

[0087] Mass spectrum: MH⁺ 196 (100)

[0088] m. 2-(2,4-Diaminobenzylamino)-propane-1-ol hydrochloride

[0089] Amine used: 2-amino-propanol

[0090] Mass spectrum: MH⁺ 196 (100)

[0091] n.1,3-Diamino-4-{[(tetrahydrofuran-2-ylmethyl)-amino]-methyl}-benzenehydrochloride

[0092] Amine used: tetrahydrofurfurylamine

[0093] Mass spectrum: MH⁺ 222 (100)

Examples 2 to 15

[0094] Hair Dyeing Agent

[0095] Hair-dyeing solutions of the following composition are prepared:1.25 mmoles developer substance of Formula (I) of Table 1 1.25 mmolescoupler substance of Table 1 1.0 g potassium oleate (8% aqueoussolution) 1.0 g ammonia (22% aqueous solution) 1.0 g ethanol 0.3 gascorbic acid ad 100.0 g water

[0096] Immediately before use, 50 g of the above dye solution are mixedwith 50 g of a 6 percent aqueous hydrogen peroxide solution.Subsequently, the mixture is applied on bleached hair. After a period ofaction of 30 minutes at 40° C., the hair is rinsed with water, washedwith a conventional, commercial shampoo and dried. The resulting dyeingsare summarized in Table 1. TABLE 1 Coupler Substance IV. III. 4,5-Coupler I. II. 2,5- diamino-1-(2′- Substance of 1,4-diamino 2,5-diamino-diaminophenyl- hydroxyethyl)- Example No. Formula (I) benzene toluenesulfate ethanol sulfate pyrazole sulfate 2. of dark blue dark blue darkblue purple Example 1a 3. of dark blue dark blue dark blue purpleExample 1b 4. of dark blue dark blue dark blue purple Example 1c 5. ofdark blue blue dark blue purple Example 1d 6. of dark blue dark bluedark blue purple Example 1e 7. of dark blue dark blue dark blue purpleExample 1f 8. of dark blue dark blue blue purple Example 1g 9. of darkblue dark blue blue purple Example 1h 10. of dark blue blue blue purpleExample 1i 11. of dark blue blue blue purple Example 1j 12. of dark blueblue blue purple Example 1k 13. of dark blue blue blue purple Example 1l14. of dark blue blue blue purple Example 1m 15. of dark blue blue bluepurple Example 1n

Examples 16 to 27

[0097] Hair Dyeing Agent

[0098] Hair-dyeing solutions of the following composition are prepared:X g 1,3-diamino-4-(aminomethyl)-benzene derivative of Formula (I)(coupler substance K1 to K3 of Table 3) U g developer substance E1 to E7of Table 2 Y g coupler substance K4 to K15 of Table 3 10.0 g potassiumoleate (8% aqueous solution) 10.0 g ammonia (22% aqueous solution) 10.0g ethanol 0.3 g ascorbic acid ad 100.0 g water

[0099] Immediately before use, 30 g of the above dye solution are mixedwith 30 g of a 6 percent aqueous hydrogen peroxide solution.Subsequently, the mixture is applied on bleached hair. After a period ofaction of 30 minutes at 40° C., the hair is rinsed with water, washedwith a conventional, commercial shampoo and dried. The resulting dyeingsare summarized in Table 5.

Examples 28 to 39

[0100] Hair Dyeing Agents

[0101] Creamy hair-dyeing compositions of the following composition areprepared: X g 1,3-diamino-4-(aminomethyl)-benzene derivative of Formula(I) (coupling substance K1 to K3 of Table 3) U g developer substance E1to E7 of Table 2 Y g coupling substance K4 to K15 of Table 3 Z gsubstantive dye D1 to D3 of Table 4 15.0 g cetyl alcohol 0.3 g ascorbicacid 3.5 g sodium lauryl alcohol diglycol ether sulfate (28% aqueoussolution) 3.0 g ammonia (22% aqueous solution) 0.3 g sodium sulfite,water-free ad 100.0 g water

[0102] Immediately before use, 30 g of the above dye solution are mixedwith 30 g of a 6 percent aqueous hydrogen peroxide solution.Subsequently, the mixture is applied on bleached hair. After a period ofaction of 30 minutes at 40° C., the hair is rinsed with water, washedwith a conventional, commercial shampoo and dried. The resulting dyeingsare summarized in Table 6.

[0103] Unless stated otherwise, all percentages, given in theapplication above, are percentages by weight. TABLE 2 DeveloperSubstances E1 1,4-diaminobenzene E2 2-(2,5-diamino-phenyl)-ethanolsulfate E3 4-amino-3-methyl-phenol E4 4-aminophenol E5N,N-bis(2-hydroxyethyl)-p-phenylenediamine E64,5-diamino-1-(2-hydroxyethyl)-pyrazole sulfate E7 2,5-diaminotoluenesulfate

[0104] TABLE 3 Coupler Substances K11,3-diamino-4-(allylaminomethyl)-benzene hydrochloride K22-(2,4-diaminobenzylamino)-ethanol hydrochloride K31,3-diamino-4-[(2-aminoethylamino)-methyl]-benzene hydrochloride K42-amino-4-(2′-hydroxyethyl)amino-anisole sulfate K51,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K61,3-bis(2,4-diaminophenoxy)propane tetrahydrochloride K7 3-amino-phenolK8 5-amino-2-methyl-phenol K9 3-amino-2-chloro-6-methyl-phenol K105-amino-4-fluoro-2-methyl-phenol sulfate K11 1-naphthol K122-amino-5-methylphenol K13 1,3-dihydroxy-benzene K142-methyl-1,3-dihydroxy-benzene K15 1-chloro-2,4-dihydroxy-benzene

[0105] TABLE 4 Direct Dyes D1 2,6-diamino-3-((pyridine-3-yl)azo)pyridineD2 6-chloro-2-ethylamino-4-nitrophenol D3 2-amino-6-chloro-4-nitrophenol

[0106] TABLE 5 Hair Dyeing Agents Example No. 16 17 18 19 20 21 Dye(amount of dye in grams) K1 0.10 0.05 0.10 0.12 K2 0.12 0.07 E1 0.30 E20.25 0.30 E7 0.25 0.30 0.25 K4 0.03 K5 0.05 K6 0.05 K7 0.05 K8 0.05 K90.05 0.10 0.10 0.10 K12 0.05 0.05 K13 0.20 0.15 0.20 0.10 K14 0.20 0.100.10 K15 0.20 Dyeing Result blond blond blond blond blond blond ExampleNo. 22 23 24 25 26 27 Dye (amount of dye in grams) K3 0.10 0.12 0.050.07 0.10 0.12 E1 0.30 E2 0.20 0.20 0.30 E3 0.10 E4 0.05 E5 0.03 E6 0.10E7 0.25 0.05 0.25 K4 0.05 K5 0.05 K6 K7 0.05 0.05 K8 0.05 K9 0.05 0.100.10 0.10 K10 0.05 K11 0.05 K12 0.30 K13 0.20 0.15 0.20 0.10 K14 0.200.10 0.10 K15 0.20 Dyeing Result blond blond rose blond blond- blondrose

[0107] TABLE 6 Hair Dyeing Agents Example No. 28 29 30 31 32 33 Dye(amount of dye in grams) K1 0.60 1.30 0.80 0.15 0.15 K2 0.15 0.15 K30.20 E1 1.00 E2 0.20 E3 0.10 E4 0.05 E5 1.60 0.70 E6 0.20 E7 1.80 0.700.70 K4 0.60 K8 0.05 K9 0.05 0.10 0.10 0.10 K10 0.05 K11 0.05 K12 0.100.05 K13 1.10 1.10 1.10 0.40 0.40 0.40 K14 K15 D1 0.05 D2 0.10 0.10 0.10D3 0.05 Dyeing Result black black black brown brown brown Example No. 3435 36 37 38 39 Dye (amount of dye in grams) K3 0.60 1.30 1.15 0.15 0.150.15 E1 1.50 E2 0.80 E5 1.60 0.70 E7 1.80 0.70 K4 0.60 K9 0.05 0.10 0.100.10 K13 1.10 1.10 1.10 0.40 0.40 0.40 D2 0.10 0.10 0.10 D3 0.10 DyeingResult black black black brown brown brown

1. 1,3-Diamino-4-(aminomethyl)-benzene derivatives of the above generalFormula (I) or their physiologically tolerated, water-soluble salts,

wherein R1 and R2 independently of one another are hydrogen, a C₁-C₆alkyl group, a C₂-C₄ hydroxyalkyl group or a C₃-C₄ dihydroxyalkyl group,R3 is hydrogen or a C₁-C₄ alkyl group, R4 and R5 independently of oneanother are hydrogen, a C₁-C₂ alkoxy group, a saturated C₁-C₆ alkylgroup, an unsaturated C₃-C₆ alkyl group, a C₂-C₄ hydroxyalkyl group, aC₃-C₄ dihydroxyalkyl group, a C₂-C₄ aminoalkyl group, a C₂-C₄dimethylaminoalkyl group, a C₂-C₄ acetylaminoalkyl group, a C₂-C₄methoxyalkyl group, a C₂-C₄ ethoxyalkyl group, a C₁-C₄ cyanalkyl group,a C₁-C₄ carboxyalkyl group, a C₁-C₄ aminocarbonylalkyl group, apyridylmethyl group, a furfuryl group, a thienyl methyl group, asubstituted pyridyl group or a group of Formula (II)

or R4 and R5 together with the nitrogen atom form a ring of Formula

R6, R7, R8, R9 and R10 independently of one another represent hydrogen,a halogen atom (F, Cl, Br, I), a cyano group, a hydroxy group, a C₁-C₄alkoxy group, a C₂-C₄ hydroxyalkoxy group, a C₁-C₆ alkyl group, a C₁-C₄alkyl thioether group, a mercapto group, a nitro group, an amino group,an alkylamino group, a di(C₁-C₆ alkyl)amino group, adihydroxy-(C₃-C₄)alkyl)amino group, a di(C₁-C₄ hydroxyalkyl)amino group,a (C₁-C₄ hydroxyalkyl)-(C₁-C₆ alkyl)-amino group, a trifluoromethanegroup, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, an —Si(CH₃)₃group, a C₁-C₄ hydroxyalkyl group, a C₂-C₄ dihydroxyalkyl group, acarboxy group or a pyrrolidine group or two R6 to R10 groups, adjacentto one another, form an —O—CH2-O link, R11 is hydrogen, a hydroxy group,a carboxy group, an aminocarbonyl group or a hydroxymethyl group; R12 ishydrogen or a C₁-C₆ alkyl group; and n is 0 or
 1. 2. The1,3-diamino-4-(aminomethyl)-benzene derivatives of claim 1, wherein oneor more or all of the R1, R2 and R3 groups of Formula (1) are hydrogen.3. The 1,3-diamino-4-(aminomethyl)-benzene derivative of claims 1 or 2,wherein one of the R4 or R5 groups in Formula (I) is a C₂-C₆hydroxyalkyl group, an unsaturated C₃-C₆ alkyl group, a C₂-C₄ aminoalkylgroup or a C₁-C₄ alkyl group.
 4. The 1,3-diamino-4-(aminomethyl)-benzenederivative of one of the claims 1 to 3, wherein it is selected from1,3-diamino-4-(methylaminomethyl)-benzene,1,3-diamino-(4-allyl-aminomethyl)-benzene,2-(2,4-diaminobenzylamino)-ethanol and1,3-diamino-4-((2-amino-ethylamino)-methyl)-benzene.
 5. An agent for theoxidative dyeing of keratin fibers, based on a combination of adeveloper and coupler substances, wherein the agent, as couplersubstances, contains at least one 1,3-diamino-4-(aminomethyl)-benzenederivative of Formula (I) of one of the claims 1 to
 4. 6. The agent ofclaim 5, wherein it contains the 1,3-diamino-4-(aminomethyl)-benzenederivative of Formula (I) in an amount of 0.005 to 20 percent by weight.7. The agent of claims 5 or 6, wherein the developer substance isselected from the group comprising 1,4-diamino-benzene,1,4-diamino-2-methyl-benzene, 1,4-diamino-2,6-dimethyl-benzene,1,4-diamino-3,5-diethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene,1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene,1,4-diamino-2-( thiophene-2-yl)-benzene,1,4-diamino-2-(thiophene-3-yl)-benzene,1,4-diamino-2-(pyridine-3-yl)-benzene, 2,5-diaminobiphenyl,1,4-diamino-2-methoxymethyl-benzene, 1,4-diamino-2-aminomethyl-benzene,1,4-diamino-2-hydroxymethyl-benzene,1,4-diamino-2-(2-hydroxyethoxy)-benzene, 2-(2-acetylamino)ethoxy)-1,4-diaminobenzene, 4-phenylamino-aniline,4-dimethylamino-aniline, 4-diethylamino-aniline, 4-dipropylamino-aniline, 4-[ethyl(2-hydroxyethyl)-amino]-aniline,4-[di(2-hydroxyethyl)amino]-aniline,4-[di(2-hydroxyethyl)-amino]-2-methyl-aniline,4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxy-propyl)amino]-aniline,4-[(2,3-dihydroxypropyl)amino]-aniline,1,4-diamino-2-(1-hydroxyethyl)-benzene,1,4-diamino-2-(2-hydroxyethyl)-benzene,1,4-diamino-2-(1-methylethyl)-benzene,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis[(4-aminophenyl)amino]-butane,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-phenol,4-amino-3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol,4-amino-3-fluoro-phenol, 4-methylamino-phenol,4-amino-2-(aminomethyl)-phenol, 4-amino-2-(hydroxymethyl)-phenol, 4-amino-2-fluoro-phenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol,4-amino-2-methyl-phenol, 4-amino-2-(methoxymethyl)-phenol,4-amino-2-(2-hydroxyethyl)-phenol, 5-amino-salicylic acid,2,5-diamino-pyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-amino-phenol,2-amino-6-methyl-phenol, 2-amino-5-methyl-phenol and1,2,4-trihydroxy-benzene.
 8. The agent of one of the claims 5 to 7,wherein, in addition to the compounds of Formula (I), it containsfurther, known coupler substances, which are selected from the groupcomprising N-(3-dimethylamino-phenyl)-urea, 2,6-diamino-pyridine,2-amino-4-[(2-hydroxyethyl)amino]-anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene,2,3-diamino-6-methoxy-pyridine,3-amino-6-methoxy-2-(methylamino)-pyridine,2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)-benzene,1,3-diamino-4-(3-hydroxy-propoxy)-benzene,1,3-diamino-4-(2-methoxyethoxy)-benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene,2,4-diamino-phenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]-aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene,5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline,3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane,di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene,2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole,3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol,5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methyl-phenol,3-amino-2-chloro-6-methyl-phenol, 3-aminophenol,2-[(3-hydroxyphenyl)-amino]-acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methyl-phenol,5-[(2-hydroxyethyl)amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxy-phenol,2-(4-amino-2-hydroxyphenoxy)-ethanol,5-[(3-hydroxypropyl)amino]-2-methyl-phenol,3-[(2,3-dihydroxypropyl)-amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine,2,6-dihydroxy-3,4-dimethyl-pyridine, 5-amino-4-chloro-2-methyl-phenol,1-naphthol, 2-methyl-l-naphthol, 1,5-dihydroxy-naphthalene,1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene,2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene,2-chloro-1,3-dihydroxy-benzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxy-phenol, 3,4-methylenedioxy-aniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole,6-hydroxy-indole, 7-hydroxy-indole and 2,3-indolindione.
 9. The agent ofone of the claims 5 to 8, wherein the developers and coupler substancesare contained in a total amount of 0.005 to 20 percent by weight, basedon the total amount of dyeing agent.
 10. The agent of one of the claims5 to 9, wherein it additionally contains at least one substantive dye.11. The agent of one of the claims 5 to 10, wherein it has a pH of 6.5to 11.5.
 12. The agent of one of the claims 5 to 11, wherein it is ahair-dyeing agent.